Humulen-trioxid

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: Humulen-trioxid
• 英文别名: humulene triepoxide；1,6,6,10-Tetramethyl-4,9,14-trioxatetracyclo[11.1.0.03,5.08,10]tetradecane；1,6,6,10-tetramethyl-4,9,14-trioxatetracyclo[11.1.0.03,5.08,10]tetradecane
• 化学式: C₁₅H₂₄O₃
• 分子量: 252.354
• InChiKey: DKHWLZDWNCVYPO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  37.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Humulen-trioxid 在 正丁基锂 、 六氯化钨 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.0h， 以57%的产率得到humulene 9,10-epoxide
  参考文献：
  名称：

  Hydrolysis and reversible isomerization of humulene epoxides II and III.

  摘要：

  The hydrolysis reactions of humulene epoxide II (3) and humulene epoxide III (4) were studied in aqueous solution at pH 4.0. Twelve compounds from the hydrolysis of humulene epoxide II and 16 from humulene epoxide III were separated and identified. All of the compounds identified from hydrolysis of 3 also were found among the hydrolysis products of 4. A reversible transformation between these two epoxides proceeding through a bicyclic diol (15) as intermediate is responsible for producing the same products. Hydrolysis reactions further yielded diols and a number of different ring systems. The apparent intermediacy of carbocations also led to several elimination reaction products. Among the products identified from these epoxides, six have not been reported before. These are 1,5,8,8-tetramethyl-12-oxa-5-tricyclo[7.2.1.0(6,9)]dodecene (1), 4,8,11,11-tetramethyl-8-tricyclo-[7.2.0.0(2,5)]undecen-4-ol (5), stereoisomers of 2,6,6,9-tetramethyltricyclo[6.3.0.0(2,4)]undecane-5,9-diol (10, 14), 1,5,8,8-tetramethyl-8-bicyclo[8.1.0]undecene-2,9-diol (15), and the stereoisomeric pair 4,8,11,11-tetramethyl-tricyclo[6.3.0.0(2,4)]undecane-5,9-diol (16).

  DOI：

  10.1021/jo00043a033
• 作为产物：
  描述：

  大麻 在 间氯过氧苯甲酸 作用下， 以 氯仿 为溶剂， 反应 15.0h， 以97%的产率得到Humulen-trioxid
  参考文献：
  名称：

  氧气在哪里？结晶海绵法分析α-Humulene氧化产物的结构

  摘要：

  通过结晶海绵法分析了α-hu草烯，环状倍半萜烯及其氧化副产物的晶体结构。区域化学和立体化学，包括使用手性氧化剂时的绝对构型，并成功测定了5-50μg规模的样品中所有与脚手架相关的化合物的稳定构象。

  DOI：

  10.1002/anie.201502302

文献信息

• Sorm et al., Collection of Czechoslovak Chemical Communications, 1949, vol. 14, p. 699,710
  作者：Sorm et al.

  DOI：——

  日期：——
• A Stable Rearrangement Product of Humulene-4,5-epoxide
  作者：Raymond M. Carman

  DOI：10.1021/np0501839

  日期：2005.9.1

  Humulene-4,5-monoepoxide, 1, may rearrange to the cyclopropyl diol 2 during chromatography over silica. The rearrangement can be reversed with acid.
• Herout et al., Collection of Czechoslovak Chemical Communications, <hi>1949</hi>, vol. 14, p. 716,721
  作者：Herout et al.

  DOI：——

  日期：——
• Hydrolysis and reversible isomerization of humulene epoxides II and III.
  作者：Xiaogen Yang、Max L. Deinzer

  DOI：10.1021/jo00043a033

  日期：1992.8

  The hydrolysis reactions of humulene epoxide II (3) and humulene epoxide III (4) were studied in aqueous solution at pH 4.0. Twelve compounds from the hydrolysis of humulene epoxide II and 16 from humulene epoxide III were separated and identified. All of the compounds identified from hydrolysis of 3 also were found among the hydrolysis products of 4. A reversible transformation between these two epoxides proceeding through a bicyclic diol (15) as intermediate is responsible for producing the same products. Hydrolysis reactions further yielded diols and a number of different ring systems. The apparent intermediacy of carbocations also led to several elimination reaction products. Among the products identified from these epoxides, six have not been reported before. These are 1,5,8,8-tetramethyl-12-oxa-5-tricyclo[7.2.1.0(6,9)]dodecene (1), 4,8,11,11-tetramethyl-8-tricyclo-[7.2.0.0(2,5)]undecen-4-ol (5), stereoisomers of 2,6,6,9-tetramethyltricyclo[6.3.0.0(2,4)]undecane-5,9-diol (10, 14), 1,5,8,8-tetramethyl-8-bicyclo[8.1.0]undecene-2,9-diol (15), and the stereoisomeric pair 4,8,11,11-tetramethyl-tricyclo[6.3.0.0(2,4)]undecane-5,9-diol (16).
• Where is the Oxygen? Structural Analysis of α-Humulene Oxidation Products by the Crystalline Sponge Method
  作者：Nicolas Zigon、Manabu Hoshino、Shota Yoshioka、Yasuhide Inokuma、Makoto Fujita

  DOI：10.1002/anie.201502302

  日期：2015.7.27

  Crystal structures of α‐humulene, a cyclic sesquiterpene, and its oxidized subproducts, were analyzed by the crystalline sponge method. Regio‐ and stereochemistry, including absolute configuration when a chiral oxidant was applied, and the stable conformations of all the scaffold‐related compounds were successfully determined for samples on a 5–50 μg scale.

  通过结晶海绵法分析了α-hu草烯，环状倍半萜烯及其氧化副产物的晶体结构。区域化学和立体化学，包括使用手性氧化剂时的绝对构型，并成功测定了5-50μg规模的样品中所有与脚手架相关的化合物的稳定构象。